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Article: Spectroscopy, molecular structure, and electrochemistry of rhenium(V) oxo and imido complexes of 1,4,8,11-tetraazacyclotetradecane (cyclam)

TitleSpectroscopy, molecular structure, and electrochemistry of rhenium(V) oxo and imido complexes of 1,4,8,11-tetraazacyclotetradecane (cyclam)
Authors
Issue Date1993
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 1993, v. 32 n. 25, p. 5827-5832 How to Cite?
Abstracttrans-[ReO2(cyclam)]ReO4·1/2H2O, trans-[ReO(OEt)(cyclam)](ClO4)2, and trans-[Re(NPh)(OH)(cyclam)](ClO4)2 (cyclam = 1,4,8,11-tetraazacyclotetradecane) were prepared and structurally characterized by X-ray crystallography. The structure of trans-[ReO2(cyclam)]ReO4·1/2H2O is quite similar to that of the previously reported trans-[ReO2-(cyclam)]Cl and trans-[ReO2(cyclam)]PF6. Crystal data: trans-[ReO2(C10H24N4)]ReO 4·1/2H2O, M = 676.74, orthorhombic, space group Pnma, a = 17.717(5) Å, b = 17.073(4) Å, c = 5.466(2) Å, V = 1653.4(9) Å3, Z = 4, dcalcd = 2.719 g cm-3, μ(Mo Kα) = 14.86 mm-1; trans-[ReO(OEt)(C10H24N4)](ClO 4)2, M = 646.49, orthorhombic, space group P212121, a = 8.869(4) Å, b = 13.850(3) Å, c = 17.681(3) Å, V = 2172(1) Å3, Z = 4, dcalcd = 1.977 g cm-3, μ(Mo Kα) = 5.97 mm-1; trans-[Re(NPh)(OH)(C10H24N4)](ClO 4)2, M = 693.55, orthorhombic, space group Pnma, a = 17.651(6) Å, b = 15.702(5) Å, c = 8.695(2) Å, V = 2410(1) Å3, Z = 4, dcalcd = 1.912 g cm-3, μ(Mo Kα) = 5.50 mm-1. The rhenium-oxo bond distances in trans-[ReO2(cyclam)]+ and trans-[ReO(OEt)-(cyclam)]2+ are 1.775(9) and 1.643(9) Å, respectively. The UV-vis spectrum of trans-[ReO2(cyclam)]+ shows two ligand field transitions at 423 and 530 nm. For trans-[ReO(OEt)(cyclam)]2+, the corresponding ligand field bands red shift to 481 and 625 nm. trans-[Re(NPh)(OH)(cyclam)]2+ is stable in aqueous medium. The measured Re≡NPh distance of 1.731(9) Å and Re≡N-Ph bond angle of 176.2(8)° are consistent with the metal-imido formulation. The cyclic voltammogram of trans-[ReO2(cyclam)]+ in aqueous medium shows a quasi-reversible 2H+-2e- couple corresponding to the reduction of Re(V) to Re(III). Both trans-[ReO(OEt)(cyclam)]2+ and trans-[Re(NPh)-(OH)(cyclam)]2+ show a 1e- reduction wave in acetonitrile at potentials of -1.0 and -1.4 V vs SCE, respectively. E° of the trans-[Rev(NPh)(OH)(cyclam)]2+/trans-[Re IV(NPh)(OH)(cyclam)]2+ couple is smaller than that of trans-[ReVO(OEt)(cyclam)]2+/trans-[Re IVO(OEt)(cyclam)]+. © 1993 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167251
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorWang, YPen_US
dc.contributor.authorChe, CMen_US
dc.contributor.authorWong, KYen_US
dc.contributor.authorPeng, SMen_US
dc.date.accessioned2012-10-08T03:04:53Z-
dc.date.available2012-10-08T03:04:53Z-
dc.date.issued1993en_US
dc.identifier.citationInorganic Chemistry, 1993, v. 32 n. 25, p. 5827-5832en_US
dc.identifier.issn0020-1669en_US
dc.identifier.urihttp://hdl.handle.net/10722/167251-
dc.description.abstracttrans-[ReO2(cyclam)]ReO4·1/2H2O, trans-[ReO(OEt)(cyclam)](ClO4)2, and trans-[Re(NPh)(OH)(cyclam)](ClO4)2 (cyclam = 1,4,8,11-tetraazacyclotetradecane) were prepared and structurally characterized by X-ray crystallography. The structure of trans-[ReO2(cyclam)]ReO4·1/2H2O is quite similar to that of the previously reported trans-[ReO2-(cyclam)]Cl and trans-[ReO2(cyclam)]PF6. Crystal data: trans-[ReO2(C10H24N4)]ReO 4·1/2H2O, M = 676.74, orthorhombic, space group Pnma, a = 17.717(5) Å, b = 17.073(4) Å, c = 5.466(2) Å, V = 1653.4(9) Å3, Z = 4, dcalcd = 2.719 g cm-3, μ(Mo Kα) = 14.86 mm-1; trans-[ReO(OEt)(C10H24N4)](ClO 4)2, M = 646.49, orthorhombic, space group P212121, a = 8.869(4) Å, b = 13.850(3) Å, c = 17.681(3) Å, V = 2172(1) Å3, Z = 4, dcalcd = 1.977 g cm-3, μ(Mo Kα) = 5.97 mm-1; trans-[Re(NPh)(OH)(C10H24N4)](ClO 4)2, M = 693.55, orthorhombic, space group Pnma, a = 17.651(6) Å, b = 15.702(5) Å, c = 8.695(2) Å, V = 2410(1) Å3, Z = 4, dcalcd = 1.912 g cm-3, μ(Mo Kα) = 5.50 mm-1. The rhenium-oxo bond distances in trans-[ReO2(cyclam)]+ and trans-[ReO(OEt)-(cyclam)]2+ are 1.775(9) and 1.643(9) Å, respectively. The UV-vis spectrum of trans-[ReO2(cyclam)]+ shows two ligand field transitions at 423 and 530 nm. For trans-[ReO(OEt)(cyclam)]2+, the corresponding ligand field bands red shift to 481 and 625 nm. trans-[Re(NPh)(OH)(cyclam)]2+ is stable in aqueous medium. The measured Re≡NPh distance of 1.731(9) Å and Re≡N-Ph bond angle of 176.2(8)° are consistent with the metal-imido formulation. The cyclic voltammogram of trans-[ReO2(cyclam)]+ in aqueous medium shows a quasi-reversible 2H+-2e- couple corresponding to the reduction of Re(V) to Re(III). Both trans-[ReO(OEt)(cyclam)]2+ and trans-[Re(NPh)-(OH)(cyclam)]2+ show a 1e- reduction wave in acetonitrile at potentials of -1.0 and -1.4 V vs SCE, respectively. E° of the trans-[Rev(NPh)(OH)(cyclam)]2+/trans-[Re IV(NPh)(OH)(cyclam)]2+ couple is smaller than that of trans-[ReVO(OEt)(cyclam)]2+/trans-[Re IVO(OEt)(cyclam)]+. © 1993 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_US
dc.relation.ispartofInorganic Chemistryen_US
dc.titleSpectroscopy, molecular structure, and electrochemistry of rhenium(V) oxo and imido complexes of 1,4,8,11-tetraazacyclotetradecane (cyclam)en_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ic00077a029-
dc.identifier.scopuseid_2-s2.0-0000061976en_US
dc.identifier.volume32en_US
dc.identifier.issue25en_US
dc.identifier.spage5827en_US
dc.identifier.epage5832en_US
dc.identifier.isiWOS:A1993ML05300030-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridWang, YP=23069213200en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridWong, KY=7404760030en_US
dc.identifier.scopusauthoridPeng, SM=35464852200en_US

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